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OrganicChemistryI
By: ChemistryDepartment, INTEC

ChapterOutline
Introduction CommonTerminologyinOrganicChemistry SystematicNomenclature Isomerism Alkanes Alkenes Halogenoalkanes Alcohols Bondingandreactivity Quantitativeorganicchemistry Appliedorganicchemistry

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Introduction
Organiccompoundsconsistofoneormore carbon b atoms t and dcontain t i functional f ti lgroups. Thefunctionalgroupdeterminesthechemical propertiesofthecompound. Examplesoforganiccompounds:alkanes, alkenes alcohols, alkenes, alcohols carboxylicacids

CommonTerminologyinOrganicChemistry
Homologousseries: aseriesofcompoundswith thesamefunctionalgroupandthesamegeneral formula,whereonememberdiffersfromthe nextbyCH2 Empiricalformula: representsthesimplestwhole number b ratio i of fatomsi inamolecule l l Molecularformula: representstheactual numberofatomsinamolecule

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Contd

CommonTerminologyinOrganic Chemistry
Structuralformula: representsthearrangementof atomsinamolecule;usuallywritteninexpanded, condensedorskeletalform

Expandedformula

Condensedformula

Skeletalformula

Contd

CommonTerminologyinOrganic Chemistry
Homolyticfission: whenabondbreakswithone electrongoingtoeachatom(formingradicals) Heterolyticfission: whenabondbreakswiththe twoelectronsgoingtoonlyoneatom Freeradical: aspeciesthathasasingleunpaired electron

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Contd

CommonTerminologyinOrganic Chemistry
Nucleophile: aspecieswhichseeksoutpositive centres,andmusthavealonepairofelectrons toformanewcovalentbond Electrophile:aspecieswhichseeksoutnegative centres,andacceptsalonepairofelectronsto formanewcovalentbond

SystematicNomenclature: Alkanes
Fromthestructuralformulaofcompound compound,findthe longestcontinuous carbonchain.Assignnamefor thischainusingcorrespondingprefixandsuffix ane.

Number of carbon atoms Prefix

Meth-

Eth-

Prop-

But-

Pent- Hex- Hept-

Oct-

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Contd

SystematicNomenclature: Alkanes
Locatealkylgroupsthatarenotpartofthe continuouschainandnamethemaccordingtothe numberofcarbonatomspresent,withsuffixyl. Thepositionofthebranchingalkylgroupis numberedfromtheparentchainsothatitsposition isatthelowestpossiblenumber. Numbersareseparatedfromeachotherbycommas andfromwordsbyhyphens.

Contd

SystematicNomenclature: Alkanes
Ifanalkanecompoundcontainstwoormore identicalbranches,thefollowingprefixesareused:
Number of branches Prefix

2 Di-

3 Tri-

4 Tetra-

Ifanalkanecompoundhastwoormoredifferent branchingalkylgroups,theyareplacedin alphabeticalorderofthename.

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Contd

SystematicNomenclature: Alkanes
Ifanalkanecompoundhasothersubstituentssuch ashalogen,itisaddedbeforethenameofthe alkaneandnumberedatthelowestposition. Iftherearetwoormoreofasimilarsubstituentsare attachedtothealkane alkane,theprefixdi,tri ortetra is addedaccordingly.

Contd

SystematicNomenclature: Alkanes
Example1:
4321

Name:2methylbutane Example2:
7654321

Name:4ethyl2,3dimethylheptane

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Contd

SystematicNomenclature: Alkanes
Example3:
8 7 4 2 1 3 5 6

Name:2,6dimethyloctane

Contd

SystematicNomenclature: Alkanes
Example4:

Name:1bromopropane

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Contd

SystematicNomenclature: Alkanes
Namethefollowingorganiccompoundusing systematicnames: 1. CH3CH2CH2CH2CH2CH3 2.
3.

Contd

SystematicNomenclature: Alkenes
Thelongestcarbonchainforalkenesmust containatleastonecarbonwithdoublebond(s). bond(s) Foralkenes,startingfrom4carbonatomsthe compoundhavetobenumberedaccordingtothe positionofdoublebond(s)inthecompound. Thenumberingshouldhavethedoublebond(s) atthelowestpossiblenumbercombination.

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Contd

SystematicNomenclature: Alkenes
Theprefixissimilarwithalkanes,butthe suffix ffi changes h t toene. Iftherearemorethanonedoublebond,the prefixdi,tri ortetra isaddedaccordingly.

Contd

SystematicNomenclature: Alkenes
Example1:
1234

Name:1,3butadiene/buta1,3diene

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Contd

SystematicNomenclature: Alkenes
Example2:
6 2 1 3 4 5

Name:2methyl2hexene/2methylhex2ene

Contd

SystematicNomenclature: Alkenes
Namethefollowingcompoundusingsystematic names.
1.

2.

3.

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Contd

SystematicNomenclature: Alcohols
For o a alcohols, co o s,the elongest o ges ca carbon bo c chain a s should ou d consistofatleastonehydroxyl(OH)group(s). Foralcohols,thesuffixisol. Startingfrom3carbonatoms,thenumberingis donesothatthehydroxylgroupisatthelowest possibleposition. Iftherearetwoormoreofhydroxylgroups,prefix di,tri ortetra isaddedaccordingly.

Contd

SystematicNomenclature: Alcohols
Example1:

Name:ethanol

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Contd

SystematicNomenclature: Alcohols
Example2:
3 2 1

Name:2propanol/propan2ol

Contd

SystematicNomenclature: Alcohols
Example3:
4 3 2 1

Name:2,3butandiol/butan2,3diol

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Contd

SystematicNomenclature: Alcohols
Namethefollowingcompoundsusing systematicnames:
1. 2. 2. 3.

Contd

SystematicNomenclature: OtherFunctionalGroups
Forotherfunctionalgroups,therulesfornaming themaresimilarwithalcohols. However,foraldehydesandcarboxylicacids,the numberingstartswiththecarbonyl/carboxylgroup. Thecarbonyl/carboxylgrouparenotusuallygiven number,unlessiftherearemorethanoneofthe samefunctionalgroups. groups Otherfunctionalgroup(s) attachedtoaldehydesorcarboxylicacidsare numbered,withthefirstcarbonisthe carbonyl/carboxylgroups.

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Contd

SystematicNomenclature: OtherFunctionalGroups
Substance Functional Group Aldehyde Ketone Carboxyli c Acid

Suffix

-al

-one

-oic acid

Contd

SystematicNomenclature: OtherFunctionalGroups
Example1:

Name:butanal

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Contd

SystematicNomenclature: OtherFunctionalGroups
Example2:
5
4 3 2 1

Name:2methylpentanal

Contd

SystematicNomenclature: OtherFunctionalGroups
Example3:
4 2 5 3 1

Name:2pentanone/pentan2one

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Contd

SystematicNomenclature: OtherFunctionalGroups
Example4:

Name:ethanoicacid

Contd

SystematicNomenclature: OtherFunctionalGroups
Example5:

3 2 1

Name:2chloropropanoicacid

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Contd

SystematicNomenclature: OtherFunctionalGroups
Namethefollowingcompoundsusingsystematic names:
1.

2.

Contd

SystematicNomenclature: OtherFunctionalGroups
Namethefollowingcompoundsusingsystematic names:
3.

4.

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Isomerism
Structuralisomers: compoundsthathave similar i il molecular l l formula f l but b tdifferent diff t structuralformula. Structuralisomersmayhave:
Differentcarbonchains(straightorbranched) Differentpositionoffunctionalgroupinthe carbonchain Differentfunctionalgroups

Contd

Isomerism
Exampleofstructuralisomers(differentcarbon chains):

pentane

2,2dimethylpropane

2methylbutane

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Contd

Isomerism
Exampleofstructuralisomers(differentposition offunctionalgroup):

1propanol

2propanol

Contd

Isomerism
Example a p eo ofst structural uctu a isomers so e s(d (different e e t functionalgroups): Molecularformula:C3H6O2

Ethyl y methanoate

P Propanoic i acid id

Methylethanoate

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Contd

Isomerism
Geometricisomers: onlyoccursifthereisa d bl bond double b di inthe th molecule, l l and deach hcarbon b hasdifferentatomsorgroupsattachedtoit. Geometricalisomershaverestrictedrotation aboutthedoublebond.

Contd

Isomerism
Exampleofgeometricisomers:

cis2butene

trans2butene

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Contd

Isomerism
Opticalisomers: existincompoundswhere4different groupsareattachedtoasinglecarbonatom. Thecarbonischiral(assymetrical). Apairoftheseisomersarecalledenantiomers andtheir mirrorimageisnotsuperimposable (ornon superimposablemirrorimage) Amixturecontainingequalamountofopticalisomersis calledaracemicmixture. mixture

Contd

Isomerism

OpticalIsomers

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Alkanes
Generalformula:CnH2n+2 1Combustionreaction:
Generalreaction: CnH2n+2 +[(3n+1)/2]O2 Example: CH4 + nCO2+(n+1)H2O

2O2

CO2

2H2O

Contd

Alkanes
2SubstitutionreactioninpresenceofUV light(Xhalogen,usuallyCl2 orBr2):
Generalreaction: CnH2n+2 + X2 CnH2n+1X+ X2

UVlight

CnH2n+1X +HX CnH2nX2 +HX

UVlight

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SubstitutionReactionofAlkanes
inpresenceofUVlight(Xhalogen,usuallyCl2 orBr B 2): ) Example: E l
CH4 CH3Cl + + Cl2 Cl2
UVlight

CH3Cl CH2Cl2

+HCl +HCl

UVlight

Contd

Alkanes
Reactionmechanism:Homolytic, Homolytic freeradical substitution 1. Initiationstep:Homolyticfissiontofreeradicals

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Contd

Alkanes
Reactionmechanism:Homolytic, Homolytic freeradical substitution 2. Propagationstep

Contd

Alkanes
Reactionmechanism:Homolytic, Homolytic freeradical substitution

2. Propagationstep

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Contd

Alkanes
Reactionmechanism:Homolytic,freeradical substitution

3. Terminationstep

Contd

Alkanes
Reactionmechanism:Homolytic,freeradical substitution

3. Terminationstep

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Contd

Alkanes
Reactionmechanism:Homolytic,freeradical addition

3. Terminationstep

Alkenes
Generalformula:CnH2n 3Additionreaction:
Withhydrogengas,at150C:
Ni/Pt/Pd

CnH2n C3H6

+ +

H2
Ni/Pt/Pd

CnH2n+2 C3H8

H2

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Alkenes
4Additionreaction:
Withhalogens,atroomtemperature(X2=Cl Cl2 or Br2): CnH2n + X2 CnH2nX2 CH3CHBrCH2Br

CH3CH=CH2 +Br2

Additionreactionofalkene
Thechangeofcolourforbromine,fromredbrown tocolourlessisatestforC=Cgroupina compound.Forthetest,bromineisdissolvedin CCl4.

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Contd

Alkenes
5Additionreaction
Withhydrogenhalides(HI/HBr),atroomtemperature: CnH2n + HX CnH2n+1X

CH3CH=CHCH3

+HBr

CH3CH2CHBrCH3

Additionreactionofalkene
Withunsymmetricalalkenes,hydrogenatomgoes tothecarbonthathasmorehydrogenatoms bondeddirectlytoit(Markovnikoffsrule).

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Contd

Alkenes Mechanism
Heterolytic,electrophilic additionreaction 1. Protonationtocarbocation:electrophilicaddition

2 Nucleophilic 2. N l hili attack tt k

2 cation morestable

1 cation

Contd

Alkenes
Additionreaction
..\abaddition.avi \ b dditi i

Minor

Major

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Contd

Alkenes
6Oxidationreaction Oxidizingagent:Potassiumpermanganate (KMnO4)inalkaline/acidiccondition,atroom temperature
CnH2n +[O]+H2O CnH2n(OH)2 CH3CH=CHCH3 +[O] +H2O CH3CH(OH)CH(OH)CH3 Potassiumpermanganatewillbereducedto manganesedioxide,whichisseenasbrown precipitate.

Contd

Alkenes
7Polymerisationreaction
.MechanismAnimated\polymerization.avi

Conditions:eitherhighpressureandtemperature (2000atm,250C) ormoderatepressureand temperaturewithcatalystaddition(10atm, 50C,catalyst:titanium(IV)chloride+triethyl aluminium) Addition Additi reaction ti nCnH2n
(CnH2n)n

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